CN107957654A - A kind of ultraviolet light for large-area nano coining cures hybrid systems coining glue - Google Patents
A kind of ultraviolet light for large-area nano coining cures hybrid systems coining glue Download PDFInfo
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- CN107957654A CN107957654A CN201711405762.XA CN201711405762A CN107957654A CN 107957654 A CN107957654 A CN 107957654A CN 201711405762 A CN201711405762 A CN 201711405762A CN 107957654 A CN107957654 A CN 107957654A
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- Prior art keywords
- parts
- coining
- glue
- hybrid systems
- coining glue
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- 239000003292 glue Substances 0.000 title claims abstract description 64
- KCTAWXVAICEBSD-UHFFFAOYSA-N prop-2-enoyloxy prop-2-eneperoxoate Chemical compound C=CC(=O)OOOC(=O)C=C KCTAWXVAICEBSD-UHFFFAOYSA-N 0.000 claims abstract description 25
- 125000005409 triarylsulfonium group Chemical group 0.000 claims abstract description 20
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 17
- UHESRSKEBRADOO-UHFFFAOYSA-N ethyl carbamate;prop-2-enoic acid Chemical compound OC(=O)C=C.CCOC(N)=O UHESRSKEBRADOO-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000004844 aliphatic epoxy resin Substances 0.000 claims abstract description 13
- 239000003085 diluting agent Substances 0.000 claims abstract description 12
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 claims description 26
- -1 Phenolic Acrylates Chemical class 0.000 claims description 23
- 229910052710 silicon Inorganic materials 0.000 claims description 22
- 239000010703 silicon Substances 0.000 claims description 22
- 239000003795 chemical substances by application Substances 0.000 claims description 19
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 18
- 239000012456 homogeneous solution Substances 0.000 claims description 16
- 238000003756 stirring Methods 0.000 claims description 16
- 239000000243 solution Substances 0.000 claims description 14
- 239000013530 defoamer Substances 0.000 claims description 12
- 239000000203 mixture Substances 0.000 claims description 11
- 239000004593 Epoxy Substances 0.000 claims description 10
- 150000001336 alkenes Chemical class 0.000 claims description 10
- 230000000694 effects Effects 0.000 claims description 10
- 229920000570 polyether Polymers 0.000 claims description 9
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 claims description 7
- 150000002148 esters Chemical class 0.000 claims description 7
- QNODIIQQMGDSEF-UHFFFAOYSA-N (1-hydroxycyclohexyl)-phenylmethanone Chemical class C=1C=CC=CC=1C(=O)C1(O)CCCCC1 QNODIIQQMGDSEF-UHFFFAOYSA-N 0.000 claims description 6
- BDAGIHXWWSANSR-UHFFFAOYSA-N Formic acid Chemical class OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 6
- 239000002253 acid Substances 0.000 claims description 5
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims description 5
- BFHIGGJUBGXSIG-UHFFFAOYSA-N C(C1CO1)OC(C1C(C(=O)O)C=CCC1)=O Chemical compound C(C1CO1)OC(C1C(C(=O)O)C=CCC1)=O BFHIGGJUBGXSIG-UHFFFAOYSA-N 0.000 claims description 4
- OKKRPWIIYQTPQF-UHFFFAOYSA-N Trimethylolpropane trimethacrylate Chemical compound CC(=C)C(=O)OCC(CC)(COC(=O)C(C)=C)COC(=O)C(C)=C OKKRPWIIYQTPQF-UHFFFAOYSA-N 0.000 claims description 4
- 150000001412 amines Chemical class 0.000 claims description 4
- 239000012895 dilution Substances 0.000 claims description 3
- 238000010790 dilution Methods 0.000 claims description 3
- XRBWKWGATZNBFW-UHFFFAOYSA-N 2-[2-(2-ethenoxyethoxy)ethoxy]ethanol Chemical class OCCOCCOCCOC=C XRBWKWGATZNBFW-UHFFFAOYSA-N 0.000 claims description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical class OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 claims description 2
- 150000001875 compounds Chemical class 0.000 claims description 2
- 239000012467 final product Substances 0.000 claims description 2
- 150000002576 ketones Chemical class 0.000 claims description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 2
- 238000002360 preparation method Methods 0.000 claims description 2
- DTTDXHDYTWQDCS-UHFFFAOYSA-N 1-phenylcyclohexan-1-ol Chemical compound C=1C=CC=CC=1C1(O)CCCCC1 DTTDXHDYTWQDCS-UHFFFAOYSA-N 0.000 claims 1
- FIHBHSQYSYVZQE-UHFFFAOYSA-N 6-prop-2-enoyloxyhexyl prop-2-enoate Chemical compound C=CC(=O)OCCCCCCOC(=O)C=C FIHBHSQYSYVZQE-UHFFFAOYSA-N 0.000 claims 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims 1
- 239000005864 Sulphur Substances 0.000 claims 1
- 150000003839 salts Chemical class 0.000 claims 1
- 230000001070 adhesive effect Effects 0.000 abstract description 8
- 230000008602 contraction Effects 0.000 abstract description 8
- 238000010526 radical polymerization reaction Methods 0.000 abstract description 8
- 239000000853 adhesive Substances 0.000 abstract description 7
- 238000010538 cationic polymerization reaction Methods 0.000 abstract description 7
- 238000007711 solidification Methods 0.000 abstract description 5
- 230000008023 solidification Effects 0.000 abstract description 5
- 239000012956 1-hydroxycyclohexylphenyl-ketone Substances 0.000 abstract description 2
- MQDJYUACMFCOFT-UHFFFAOYSA-N bis[2-(1-hydroxycyclohexyl)phenyl]methanone Chemical compound C=1C=CC=C(C(=O)C=2C(=CC=CC=2)C2(O)CCCCC2)C=1C1(O)CCCCC1 MQDJYUACMFCOFT-UHFFFAOYSA-N 0.000 abstract description 2
- 230000002708 enhancing effect Effects 0.000 abstract description 2
- 230000006872 improvement Effects 0.000 abstract description 2
- 238000001723 curing Methods 0.000 description 18
- 239000000463 material Substances 0.000 description 17
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 13
- 229940106691 bisphenol a Drugs 0.000 description 12
- 238000000034 method Methods 0.000 description 12
- 238000004519 manufacturing process Methods 0.000 description 9
- 239000000758 substrate Substances 0.000 description 9
- 230000008901 benefit Effects 0.000 description 8
- 150000001768 cations Chemical class 0.000 description 8
- 238000000016 photochemical curing Methods 0.000 description 7
- 150000003254 radicals Chemical class 0.000 description 7
- CYIGRWUIQAVBFG-UHFFFAOYSA-N 1,2-bis(2-ethenoxyethoxy)ethane Chemical compound C=COCCOCCOCCOC=C CYIGRWUIQAVBFG-UHFFFAOYSA-N 0.000 description 6
- 150000001335 aliphatic alkanes Chemical class 0.000 description 6
- 238000005516 engineering process Methods 0.000 description 5
- 230000008569 process Effects 0.000 description 5
- 230000008859 change Effects 0.000 description 4
- 238000000576 coating method Methods 0.000 description 4
- 239000002086 nanomaterial Substances 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- ZXHDVRATSGZISC-UHFFFAOYSA-N 1,2-bis(ethenoxy)ethane Chemical compound C=COCCOC=C ZXHDVRATSGZISC-UHFFFAOYSA-N 0.000 description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 3
- 239000003999 initiator Substances 0.000 description 3
- 238000001459 lithography Methods 0.000 description 3
- 229920005989 resin Polymers 0.000 description 3
- 239000011347 resin Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 241000209094 Oryza Species 0.000 description 2
- 235000007164 Oryza sativa Nutrition 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- 238000003848 UV Light-Curing Methods 0.000 description 2
- QYKIQEUNHZKYBP-UHFFFAOYSA-N Vinyl ether Chemical class C=COC=C QYKIQEUNHZKYBP-UHFFFAOYSA-N 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 230000005764 inhibitory process Effects 0.000 description 2
- 238000000025 interference lithography Methods 0.000 description 2
- 230000002045 lasting effect Effects 0.000 description 2
- 238000001127 nanoimprint lithography Methods 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 2
- 229920000647 polyepoxide Polymers 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 230000009257 reactivity Effects 0.000 description 2
- 235000009566 rice Nutrition 0.000 description 2
- 150000004756 silanes Chemical class 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- NNNLYDWXTKOQQX-UHFFFAOYSA-N 1,1-di(prop-2-enoyloxy)propyl prop-2-enoate Chemical compound C=CC(=O)OC(CC)(OC(=O)C=C)OC(=O)C=C NNNLYDWXTKOQQX-UHFFFAOYSA-N 0.000 description 1
- 239000004925 Acrylic resin Substances 0.000 description 1
- 206010054949 Metaplasia Diseases 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 1
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 1
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 1
- 239000007983 Tris buffer Substances 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 125000002723 alicyclic group Chemical group 0.000 description 1
- 238000012648 alternating copolymerization Methods 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 238000012656 cationic ring opening polymerization Methods 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 230000002079 cooperative effect Effects 0.000 description 1
- BMFYCFSWWDXEPB-UHFFFAOYSA-N cyclohexyl(phenyl)methanone Chemical compound C=1C=CC=CC=1C(=O)C1CCCCC1 BMFYCFSWWDXEPB-UHFFFAOYSA-N 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 125000005520 diaryliodonium group Chemical group 0.000 description 1
- 239000012954 diazonium Substances 0.000 description 1
- 150000002009 diols Chemical class 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 229940052303 ethers for general anesthesia Drugs 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000009775 high-speed stirring Methods 0.000 description 1
- 238000001746 injection moulding Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 230000015689 metaplastic ossification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- YCWSUKQGVSGXJO-NTUHNPAUSA-N nifuroxazide Chemical group C1=CC(O)=CC=C1C(=O)N\N=C\C1=CC=C([N+]([O-])=O)O1 YCWSUKQGVSGXJO-NTUHNPAUSA-N 0.000 description 1
- 239000004843 novolac epoxy resin Substances 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 230000008520 organization Effects 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 238000001259 photo etching Methods 0.000 description 1
- 238000000206 photolithography Methods 0.000 description 1
- 229920002120 photoresistant polymer Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- 230000008439 repair process Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000005348 self-cleaning glass Substances 0.000 description 1
- 150000003376 silicon Chemical class 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000004528 spin coating Methods 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 229960000834 vinyl ether Drugs 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 238000004383 yellowing Methods 0.000 description 1
Classifications
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
Abstract
The invention discloses a kind of ultraviolet light for large-area nano coining to cure hybrid systems coining glue, is made of the component of following parts by weight：10~60 parts of aliphatic epoxy resin, 5~15 parts of epoxy acrylate, 0~10 part of urethane acrylate, 20~40 parts of reactive diluent, 1~15 part of photoinitiator, 0~5 part of auxiliary agent, the photoinitiator include triaryl sulfonium salts and 1 hydroxy-cyclohexyl phenyl ketone.The coining glue of the present invention is cationic polymerization and the coining glue of radical polymerization hybrid systems, wherein, account for Main Components in cationic polymerization system, radical polymerization system belongs to enhancing item, for improving the solidification rate of coining glue, the adhesion after improvement coining adhesive curing with mould, is easy to demould.During curing, it is low to imprint the cubical contraction of glue, imprints precision and quality is high.
Description
Technical field
The present invention relates to a kind of impression materials, more particularly to a kind of ultraviolet light for large-area nano coining, which cures, to be mixed
System imprints glue.
Background technology
High definition FPD, high performance solar panels, antireflection and self-cleaning glass, LED are graphical, wafer scale micro-nano
The fields such as optics have very to improve the performance of product and quality for large area micro-nano pattern technology
Huge industry demand, the common trait of these products are needed in large scale non-smooth rigid substrate (hard substrate or base
Plate) or frangible substrate on produce efficiently at low cost large area and complexity three-dimensional micro-nano structure.It is however, existing
No matter various micro-nano manufacturing technologies (beamwriter lithography, optical lithography, laser interference lithography, holographic lithography etc.) are in technology
Aspect (non-smooth surface/substrate large area micro-nano is graphical) or production cost and efficiency etc. all suffer from it is many not
Foot and limitation, are also difficult to the actual requirement for meeting the production of industrial scale metaplasia at present.
Nano-imprint lithography (Nanoimprint Lithography, NIL) is as a kind of brand-new micro-nano manufacturing technology
(micro-nano graph clone method), than existing projection lithography and Next Generation Lithography, has high resolution, Ultra Low Cost
(NIL of the equal production technique of internal authority organization evaluation is than traditional optical projection photoetching at least order of magnitude lower) and high production
The characteristics of rate, and its most significant advantage is large area, the ability of complex three-dimensional micro-nano structure manufacture and non-smooth lining
Bottom is graphical, especially the ultraviolet nanometer imprint process with reference to soft mold also have non-smooth (bending, warpage or step),
The patterned prominent potential of large area micro-nano rice is realized on curved surface, frangible substrate.
Large-area nano stamping technique includes four technical factors：Embosser, impression materials, mould, technique, wherein work
Efficiency that one of skill key element impression materials (coining glue) are imprinted for large-area nano, precision, the quality of coining pattern have non-
Often important influence.Large-area nano stamping technique requires impression materials to possess following performance requirement：(1) curing rate is fast；(2)
It is adapted to the large area coating methods such as slot coated, spraying；(3) it is adapted to imprint under room temperature and atmospheric environment；(4) jail is sticked with base material
Gu；(5) it is adapted to the large area micro-nano structure demoulding；(6) the quick and complete filling of large area micro-nano structure can be realized.It is and most of at present
Nano-imprinting materials cannot meet the performance requirement of large-area nano coining at the same time.Therefore, it is necessary to develop new photoresist, meet
The Practical Project demand of large-area nano coining.
According to the difference of Photoinitiated reactions mechanism, coining glue is divided into two big system of free radical and cationic polymerization.Receive at present
The widely used coining glue of rice coining is mainly acrylic type ultraviolet stamping glue, it belongs to radical polymerization system, free radical light
Curing has the advantages that curing rate fast (can be fully cured in several seconds), easy mold release, low-cost, but resin viscosity is high, curing
Volume contraction is big, and oxygen inhibition easily occurs, and cured film is poor to substrate adhesive property.Glue, sun are imprinted different from radical polymerization system
Ion light-cured type imprints glue, have the advantages that cubical contraction is low, resin viscosity is low after curing, can solidify afterwards, but cure fast
Degree is slow, one-step solidification degree is low, cure after cementability it is too strong cause to be difficult to demould, to water vapor sensitive the problems such as.Free radical light is consolidated
Change or the actual requirement that can not all meet large-area nano coining well is used alone in cation photocuring.
Free radical and cation mixed system impression materials can give full play to the advantages of respective, make up the shortcomings that respective,
Optimize etc. in light-initiated, volume contraction, performance and produce good cooperative effect, disclosure satisfy that large-area nano coining for
The various performance requirements of impression materials.But it is presently mainly acrylate/epoxy resin and third for hybrid UV curable paint
Olefin(e) acid ester/vinyl ethers hybrid systems, and component is suitable more based on radically curing component or both, while contain in system
Volatile solvents, easily pollute environment, and operating personnel are caused with certain toxic action.Such hybrid UV-curing
System impression materials still suffer from speed of imprint, precision, quality, powder injection molding etc. when being imprinted for large-area nano, and there are all
It is more insufficient.It cannot meet the performance requirement of large-area nano coining.Therefore, there is an urgent need to develop meet large-area nano coining work
The novel hybrid system impression materials of skill.
The content of the invention
For above-mentioned technical problem existing in the prior art, the object of the present invention is to provide one kind to be used for large-area nano
The ultraviolet light of coining cures hybrid systems coining glue, to solve in large-area nano imprints manufacturing process, tradition coining colloidality
Can be single, curing rate, stripping result, cannot be same with the comprehensive performance such as base material adhesion, cubical contraction and environmental suitability
When meet the technical requirements of large-area nano imprint process.Overcome conventional free radical photocuring coining adhesive curing speed fast, easily de-
Mould, but volume contraction is big, oxygen inhibition easily occurs, is poor with substrate adhesion effect；Cation photocuring coining glue volume contraction it is small, with
The problem of substrate adhesiving effect is good, but curing rate is slow, the hardly possible demoulding.
In order to solve the above technical problems, the technical scheme is that：
A kind of ultraviolet light for large-area nano coining cures hybrid systems coining glue, by the component group of following parts by weight
Into：
10~60 parts of aliphatic epoxy resin, 5~15 parts of epoxy acrylate, 0~10 part of urethane acrylate, activity
20~40 parts of diluent, 1~15 part of photoinitiator, 0~5 part of auxiliary agent, the photoinitiator include triaryl sulfonium salts and 1- hydroxyls
Base cyclohexyl phenyl ketone.
Preferably, the ultraviolet light for large-area nano coining cures hybrid systems coining glue, by following parts by weight
Component composition：20~50 parts of aliphatic epoxy resin, 10~15 parts of epoxy acrylate, 1~8 part of urethane acrylate,
20~30 parts of reactive diluent, 1~10 part of photoinitiator, 1~5 part of auxiliary agent.
It is further preferred that the ultraviolet light for large-area nano coining cures hybrid systems coining glue, by following
The component composition of parts by weight：50 parts of aliphatic epoxy resin, 10 parts of epoxy acrylate, 1 part of urethane acrylate, activity are dilute
Release 30 parts of agent, 6 parts of photoinitiator, 3 parts of auxiliary agent.
Preferably, the aliphatic epoxy resin is selected from following one or more kinds of compositions：3,4- epoxies
Cyclohexyl methyl -3,4- epoxycyclohexyls formic acid esters, double ((3,4- epoxycyclohexyls) methyl) adipate esters, tetrahydrochysene O-phthalic
Sour 2-glycidyl ester.
Preferably, the epoxy acrylate is selected from following one or more kinds of compositions：Bisphenol-A epoxy third
Olefin(e) acid ester, Epoxy Phenolic Acrylates, amine modified epoxy acrylic ester, organic silicon modified epoxy acrylate.
Preferably, the mass ratio of triaryl sulfonium salts and 1- hydroxy-cyclohexyl phenyl ketones is 4~8:1.
Preferably, the reactive diluent is triethylene glycol vinyl ethers, 1,6- hexanediyl esters or trihydroxy methyl
One or more kinds of mixtures in propane triacrylate.
Preferably, the auxiliary agent is levelling agent and defoamer.Levelling agent improves effectively to reduce coining glue surface tension
The material of its levelability and uniformity.Defoamer is used for the surface tension for reducing coining glue, suppresses coining glue and produces or eliminate pressure
Print the material that glue produces foam.
It is further preferred that the levelling agent is organosilicon alkyl compound, the defoamer gathers for organic silicon or silicon
Ether compound.
The ultraviolet light cures the preparation method of hybrid systems coining glue, includes the following steps：
1) triaryl sulfonium salts photoinitiator is instilled in reactive diluent with setting speed, has then added 1- hydroxyls ring
Base phenyl ketone, is stirred at the same time, forms it into homogeneous solution I；
2) aliphatic epoxy resin and epoxy acrylate are added in solution I, homogeneous solution II is formed after stirring；
3) auxiliary agent is added into solution II while stirring, glue is imprinted to obtain the final product after stirring setting time.
Above-mentioned ultraviolet light cures application of the hybrid systems coining glue in large-area nano coining.
The effect of each component in the coining glue of this hair invention：
Aliphatic epoxy resin is film forming matter, is determine ultraviolet light solidified imprinting glue physical mechanical property main group
Part, many important performances to imprinting glue, such as rigidity, viscosity, curing rate, adhesive force, pliability, water-resistance, etch resistant properties
Etc. having a great impact.Aliphatic epoxy resin can carry out cationic ring-opening polymerization, and it is preferable can to assign coining glue
Hardness and etch resistance, by adjusting the segmented structure between alicyclic ring, make coining glue have certain pliability at the same time, easy to solid
The brittle failure of minutiae part will not be caused when being demoulded after change.
Reactive diluent is a kind of organic molecule containing polymerizable functional group, it not only dissolves and dilute oligomer,
The viscosity of regulation system, and Light Curing is participated in, influence to imprint the photo-curing rate of glue and the various performances of cured film.Second
Alkene ether reactivity is high, can carry out radical polymerization, cationic polymerization and charge-transfer complex alternating copolymerization.Therefore, second
Alkene ether can use in radical UV curing system, Cationic curing systems and hybrid systems as reactive diluent.At the same time
Since vinyl ethers is with very low viscosity and with preferable dilution effect, it can make coining glue that there is relatively low viscosity, from
And it is convenient for the spin processes of spin coating.Medium vinyl ether of the present invention selects triethylene glycol divinyl ether.1,6-HD dipropyl
Olefin(e) acid ester viscosity is low, and dilution capacity is strong, can improve the pliability of cured film.Trimethylolpropane trimethacrylate viscosity is larger,
But it is minimum one kind in polyfunctional group reactive diluent, the photo-curing rate of curing system can be improved.
Epoxy acrylate is most widely used at present, Photocurable oligomers that dosage is maximum, is had higher rigid, strong
Degree and heat endurance, while be conducive to the attachment of polar substrates.Epoxy acrylate is selected from following a kind of or a kind of in the present invention
Composition above：It is bisphenol A epoxy acrylate, Epoxy Phenolic Acrylates, amine modified epoxy acrylic ester, organic-silicon-modified
Epoxy acrylate.Bisphenol A epoxy acrylate is the most fast one kind of photo-curing rate in oligomer, and cured film has hardness
Greatly, high glaze, chemical resistance be excellent, preferable heat resistance and electrical property, while the hydroxyl of side chain is conducive to polar group
The attachment of material.Novolac epoxy resin is than bisphenol A epoxy acrylate reactivity higher, crosslink density bigger, its cured film tool
Have the advantages that big hardness, high glaze, chemical proofing are excellent.Amine modified epoxy acrylic ester can improve photo-curing rate,
Improve brittleness and adhesive force.Organic silicon modified epoxy acrylate can improve weatherability, heat resistance, wearability and soil resistance.
Urethane acrylate (PUA) makes cured film have excellent wearability and pliability, and fracture extension rate is high, at the same time
With good chemical proofing and high- and low-temperature resistance performance, preferable impact resistance.Urethane acrylate is that current light is consolidated
A very important quasi-oligomer in change field, not only possesses the advantages that polyurethane wear resistant is good, flexible, while have both third
The weatherability of olefin(e) acid ester, the advantages that adhesive force is good, and synthesis technique is simple, performance that can be by MOLECULE DESIGN method to resin
It is adjusted.The synthesis of urethane acrylate is to utilize isocyano-NCO and long chain diol and acrylic acid hydroxyl in the present invention
Hydroxyl-OH reactions, form ammonia ester bond-NHCOO-(carbamate) and are made in base ester.
Photoinitiator includes cation light initiator and free radical photo-initiation.Aryl salt mainly includes Diaryl iodonium
Salt and triaryl sulfonium salts, are current most ripe, the most widely used cation light initiators of research.Such initiator overcomes
The shortcomings that aryl diazonium salts, and there is good photonasty, heat endurance and space charge force, the compatibility with various monomers
It is good, it is applied widely.The heat endurance of triaryl sulfonium salts is more preferable than diaryl group iodized salt, is heated to 300 DEG C and does not also decompose, with
Reactive diluent Hybrid Heating will not trigger polymerization, therefore system stable upon storage is more preferable.1- hydroxy-cyclohexyl phenyl first
Ketone, which has, very high space charge force, excellent heat endurance and does not produce xanthochromia, be domestic most common photoinitiator it
One, maximum absorption wavelength 333nm, are mainly used for triggering the rapid curing of the system such as acrylate and methacrylate.
Auxiliary agent is to manufacture to imprint glue, improving coating and ink performance in construction application and transport storage process
And the additive used.The auxiliary agent of the present invention includes organic silanes levelling agent, defoamer.
The present invention advantageous effects be：
1) coining glue of the invention is cationic polymerization and the coining glue of radical polymerization hybrid systems, wherein, cation
Main Components are accounted in polymerization system, radical polymerization system belongs to enhancing item, for improving the solidification rate of coining glue, improves pressure
Adhesion after print adhesive curing with mould, is easy to demould.During curing, it is low to imprint the cubical contraction of glue, imprints precision and quality
It is high.
2) the coining adhesive curing time of the invention is short, and coining is efficient, good with base material adhesion, overcomes large-area nano pressure
Stamping structure and base material segregative defect during the print demoulding.
3) the antioxygen resistance ability of coining glue of the invention is strong, can under room temperature atmospheric environment rapid curing, simplify and set
For structurally and operationally.
4) coining glue of the invention has glossiness height, the high advantage of index of refraction, transmitance.
5) volatile solvents are free of in coining glue of the invention, therefore are not present caused by solvent volatilizees cured film
Influence and the harm to environment.
Embodiment
It is noted that described further below is all illustrative, it is intended to provides further instruction to the application.It is unless another
Indicate, all technical and scientific terms used herein has usual with the application person of an ordinary skill in the technical field
The identical meanings of understanding.
It should be noted that term used herein above is merely to describe embodiment, and be not intended to restricted root
According to the illustrative embodiments of the application.As used herein, unless the context clearly indicates otherwise, otherwise singulative
It is also intended to include plural form, additionally, it should be understood that, when in the present specification using term "comprising" and/or " bag
Include " when, it indicates existing characteristics, step, operation, device, component and/or combinations thereof.
Embodiment 1
A kind of coining glue is provided, is made of the component of following parts by weight：
3,4- 50 parts of epoxycyclohexyl-methyl -3,4- epoxycyclohexyl formic acid esters, 10 parts of bisphenol A epoxy acrylate, three
30 parts of ethylene glycol divinyl ether, 6 parts of triaryl sulfonium salts, 1 part of 1- hydroxy-cyclohexyls phenyl ketone, organic silicon or silicon polyethers
1 part of defoamer, 2 parts of organosilicon alkanes levelling agent.
Triaryl sulfonium salts are chosen first as photoinitiator, and photoinitiator is 6 parts, then chooses 30 parts of triethylene glycol diethyl
Alkene ether, photoinitiator triaryl sulfonium salts are placed in constant pressure funnel and are added dropwise to triethylene glycol divinyl ether with certain speed
In, 1 part of 1- hydroxy-cyclohexyl phenyl ketones are added, while blender high-speed stirred is started, formed after 30 minutes uniform
Solution I；Again respectively choose 50 parts 3,4- epoxycyclohexyl-methyl -3,4- epoxycyclohexyls formic acid esters, 10 parts of bisphenol-A epoxy
Acrylate is added in solution I, then homogeneous solution II is formed when high-speed stirred 2 is small, adds 1 part organic while stirring afterwards
Silicon class or silicon polyethers defoamer and 2 parts of organosilicon alkanes levelling agents, ultraviolet light is can obtain after adding auxiliary agent when stirring 2 is small
Solidification cation type imprints glue.
Embodiment 2
A kind of coining glue is provided, is made of the component of following parts by weight：
40 parts of tetrahydrophthalic acid 2-glycidyl ester, 10 parts of bisphenol A epoxy acrylate, triethylene glycol divinyl ether
40 parts, 6 parts of triaryl sulfonium salts, 1 part of 1- hydroxy-cyclohexyls phenyl ketone, 1 part of organic silicon or silicon polyethers defoamer are organic
2 parts of silanes levelling agent.
Triaryl sulfonium salts are chosen first as photoinitiator, and photoinitiator is 6 parts, then chooses 40 parts of triethylene glycol diethyl
Alkene ether, photoinitiator triaryl sulfonium salts are placed in constant pressure funnel and are added dropwise to triethylene glycol divinyl ether with certain speed
In, 1 part of 1- hydroxy-cyclohexyl phenyl ketones are added, while blender high-speed stirred is started, formed after 30 minutes uniform
Solution I；40 parts of tetrahydrophthalic acid 2-glycidyl ester is chosen respectively again, 10 parts of bisphenol A epoxy acrylate adds
Into solution I, then homogeneous solution II is formed when high-speed stirred 2 is small, add 1 part of organic silicon or silicon polyethers while stirring afterwards
Class defoamer and 2 parts of organosilicon alkanes levelling agents, ultraviolet ray solidification cation type is can obtain after adding auxiliary agent when stirring 2 is small
Imprint glue.
Embodiment 3
A kind of coining glue is provided, is made of the component of following parts by weight：
3,4- 36 parts of epoxycyclohexyl-methyl -3,4- epoxycyclohexyl formic acid esters, 12 parts of bisphenol A epoxy acrylate, gathers
4 parts of urethane acrylate, 35 parts of triethylene glycol divinyl ether, 1,6- 1.3 parts of hexanediyl ester, trimethylolpropane tris
1.3 parts of acrylate, 7 parts of triaryl sulfonium salts, 2 parts of 1- hydroxy-cyclohexyls phenyl ketone, organic silicon or the defoaming of silicon polyethers
0.4 part of agent, 1 part of organosilicon alkanes levelling agent.
Photoinitiator of 7 parts of the triaryl sulfonium salts as cationic polymerization system is chosen first, then chooses the three of 35 parts
Ethylene glycol divinyl ether, photoinitiator triaryl sulfonium salts are placed in constant pressure funnel and are added dropwise to triethylene glycol diethyl with certain speed
In alkene ether, while blender high-speed stirred is started, homogeneous solution I is formed after 30 minutes；Choose 36 parts of 3,4- respectively again
Epoxycyclohexyl-methyl -3,4- epoxycyclohexyl formic acid esters is added in solution I, then when high-speed stirred 2 is small forms homogeneous solution
II；Choose gross weight than be respectively 1.3 parts 1,6- hexanediyl esters, 1.3 parts of trimethylolpropane trimethacrylate,
It is placed in same device, starts blender high-speed stirred, then chooses 2 parts of 1- hydroxy-cyclohexyl phenyl ketones and be placed in constant pressure
In funnel, 1- hydroxy-cyclohexyls phenyl ketone is added dropwise in device with certain speed, at the same lasting stirring, high-speed stirred half
Homogeneous solution III is formed after hour, then choose 12 parts bisphenol A epoxy acrylate and 4 parts of urethane acrylate it is mixed
Compound adding apparatus high speed stirs, be stirred 2 it is small when after form homogeneous solution IV.It is high that solution IV is finally added into solution II
Speed stirring 2 forms homogeneous solution V when small, adds organic silicon of the gross weight than 0.4 part or the defoaming of silicon polyethers while stirring afterwards
Agent and 1 part of organosilicon alkanes levelling agent, add be stirred for after auxiliary agent 2 it is small when can obtain the hybrid systems coining of UV light
Glue.
Embodiment 4
Embodiment 4 provides a kind of coining glue, is made of the component of following parts by weight：
36 parts of tetrahydrophthalic acid 2-glycidyl ester, 12 parts of bisphenol A epoxy acrylate,
4 parts of urethane acrylate, 35 parts of triethylene glycol divinyl ether, 1,6- 1.3 parts of hexanediyl ester, three hydroxyls
1.3 parts of propane tri, 7 parts of triaryl sulfonium salts, 2 parts of 1- hydroxy-cyclohexyls phenyl ketone, organic silicon or silicon
0.4 part of polyethers defoamer, 1 part of organosilicon alkanes levelling agent.
Photoinitiator of 7 parts of the triaryl sulfonium salts as cationic polymerization system is chosen first, then chooses the three of 35 parts
Ethylene glycol divinyl ether, photoinitiator triaryl sulfonium salts are placed in constant pressure funnel and are added dropwise to triethylene glycol diethyl with certain speed
In alkene ether, while blender high-speed stirred is started, homogeneous solution I is formed after 30 minutes；Choose 36 parts of tetrahydrochysene respectively again
O-phthalic acid diglycidyl ester is added in solution I, then homogeneous solution II is formed when high-speed stirred 2 is small；Choose gross weight ratio
Respectively 1.3 parts of 1,6- hexanediyl esters, 1.3 parts of trimethylolpropane trimethacrylate, are placed on same
In device, blender high-speed stirred is started, then chooses 2 parts of 1- hydroxy-cyclohexyl phenyl ketones and is placed in constant pressure funnel, by 1-
Hydroxy-cyclohexyl phenyl ketone is added dropwise in device with certain speed, while lasting stirring, high-speed stirred are formed after half an hour
Homogeneous solution III, then choose 12 parts of bisphenol A epoxy acrylate and the mixture addition dress of 4 parts of urethane acrylate
Put high speed stirring, be stirred 2 it is small when after form homogeneous solution IV.It is small that solution IV is finally added into solution II high-speed stirred 2
When formed homogeneous solution V, afterwards while stirring add 0.4 part organic silicon or silicon polyethers defoamer and 1 part of organosilan
Class levelling agent, add be stirred for after auxiliary agent 2 it is small when can obtain the hybrid systems coining glue of UV light.
Various performance tests are carried out to above-mentioned four kinds coining glue, the result is shown in table 1.
Table 1
As shown in Table 1, coining glue of the invention is short, attached to base material with non-volatility solvent, low-shrinkage, hardening time
Put forth effort that high, antioxygen resistance ability is strong, non yellowing, glossiness are high, index of refraction, the features such as transmitance is high, be adapted to slot coated, blade coating etc.
Large area coating method, the coining glue comprehensive performance meet the requirement of large-area nano imprint process.It is a kind of towards large area
The ultraviolet light solidified imprinting glue of the function admirable of nano impression.
The foregoing is merely the preferred embodiment of the application, the application is not limited to, for the skill of this area
For art personnel, the application can have various modifications and variations.It is all within spirit herein and principle, made any repair
Change, equivalent substitution, improvement etc., should be included within the protection domain of the application.
Claims (10)
1. a kind of ultraviolet light for large-area nano coining cures hybrid systems coining glue, it is characterised in that：By following weight
The component composition of part：
10~60 parts of aliphatic epoxy resin, 5~15 parts of epoxy acrylate, 0~10 part of urethane acrylate, activity dilution
20~40 parts of agent, 1~15 part of photoinitiator, 0~5 part of auxiliary agent, the photoinitiator include triaryl sulfonium salts and 1- hydroxyl rings
Base phenyl ketone.
2. ultraviolet light according to claim 1 cures hybrid systems coining glue, it is characterised in that：By the group of following parts by weight
It is grouped into：20~50 parts of aliphatic epoxy resin, 10~15 parts of epoxy acrylate, 1~8 part of urethane acrylate, activity
20~30 parts of diluent, 1~10 part of photoinitiator, 1~5 part of auxiliary agent.
3. ultraviolet light according to claim 2 cures hybrid systems coining glue, it is characterised in that：By the group of following parts by weight
It is grouped into：50 parts of aliphatic epoxy resin, 10 parts of epoxy acrylate, 1 part of urethane acrylate, 30 parts of reactive diluent,
6 parts of photoinitiator, 3 parts of auxiliary agent.
4. hybrid systems coining glue is cured according to any ultraviolet lights of claim 1-3, it is characterised in that：The aliphatic
Epoxy resin is selected from following one or more kinds of compositions：3,4- epoxycyclohexyl-methyl -3,4- epoxycyclohexyls
Formic acid esters, double ((3,4- epoxycyclohexyls) methyl) adipate esters, tetrahydrophthalic acid 2-glycidyl ester.
5. hybrid systems coining glue is cured according to any ultraviolet lights of claim 1-3, it is characterised in that：The epoxy third
Olefin(e) acid ester is selected from following one or more kinds of compositions：Bisphenol A epoxy acrylate, Epoxy Phenolic Acrylates,
Amine modified epoxy acrylic ester, organic silicon modified epoxy acrylate.
6. hybrid systems coining glue is cured according to any ultraviolet lights of claim 1-3, it is characterised in that：Triaryl sulphur
The mass ratio of salt and 1- hydroxy-cyclohexyl phenyl ketones is 4~8:1.
7. hybrid systems coining glue is cured according to any ultraviolet lights of claim 1-3, it is characterised in that：The activity is dilute
Agent is released as one kind or one in triethylene glycol vinyl ethers, 1,6 hexanediol diacrylate or trimethylolpropane trimethacrylate
The mixture of the kind above.
8. hybrid systems coining glue is cured according to any ultraviolet lights of claim 1-3, it is characterised in that：The auxiliary agent is
Levelling agent and defoamer, the levelling agent are organosilicon alkyl compound, and the defoamer is organic silicon or silicon polyethers
Compound.
9. any ultraviolet lights of claim 1-8 cure the preparation method of hybrid systems coining glue, it is characterised in that：Including such as
Lower step：
1) triaryl sulfonium salts photoinitiator is instilled in reactive diluent with setting speed, then adds 1- hydroxy-cyclohexyl benzene
Base ketone, is stirred at the same time, forms it into homogeneous solution I；
2) aliphatic epoxy resin and epoxy acrylate are added in solution I, homogeneous solution II is formed after stirring；
3) auxiliary agent is added into solution II while stirring, glue is imprinted to obtain the final product after stirring setting time.
10. any ultraviolet lights of claim 1-8 cure application of the hybrid systems coining glue in large-area nano coining.
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| CN112778822A (en) * | 2021-01-06 | 2021-05-11 | 厦门三德信科技股份有限公司 | Cover plate ink based on cationic photoinitiator and preparation method thereof |
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